CN114394884A - Preparation method of allyl phenol compound - Google Patents
Preparation method of allyl phenol compound Download PDFInfo
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- CN114394884A CN114394884A CN202111487408.2A CN202111487408A CN114394884A CN 114394884 A CN114394884 A CN 114394884A CN 202111487408 A CN202111487408 A CN 202111487408A CN 114394884 A CN114394884 A CN 114394884A
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- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
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- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The invention discloses a preparation method of allyl phenol compounds, which comprises the steps of reacting a mixed reaction system containing a diazoquinone compound, allyl borate, a catalyst and a solvent at room temperature in a protective atmosphere, and then separating to prepare allyl alcoholPhenol compounds. Diazoquinone compounds and allyl boric acid ester in the invention are used as catalyst Rh2(esp)2Under the catalysis of the method, the allyl phenol compound can be quickly and efficiently synthesized only under the conditions of room temperature and normal pressure, the reaction yield can reach more than 85 percent, and the highest yield can reach 94 percent; and the reaction only produces allyl phenol compounds with single structures; therefore, the invention obviously reduces the reaction temperature for synthesizing the allyl phenol compound, and can be carried out efficiently only at room temperature (23 +/-2) DEG C; meanwhile, the yield of the allylphenol compound and the regioselectivity of the reaction are obviously improved.
Description
Technical Field
The invention relates to the field of organic synthesis, and in particular relates to a preparation method of an allylphenol compound.
Background
Allylphenol is an important structural motif present in a wide range of natural compounds with a range of biological and pharmacological activities. For example, Honokiol and γ -Mangostin have been found to possess a variety of biological activities, including anti-cancer and anti-viral properties. Cathafurans exhibit antibacterial, antioxidant, anti-inflammatory and cytotoxic activity. Pestalone is reported to exhibit potent antibiotic activity against Staphylococcus aureus and to be cytotoxic to various tumor cells. Petalostemumol G5 and Obtustyrene showed that the antibacterial property Pestalachloride A is an antifungal compound.
Claisen rearrangement of allyl phenyl ether and Friedel-Craft type allylation of phenols are two common methods of synthesizing allyl phenol compounds. Although these two methods allow the direct synthesis of allylphenol compounds from simple starting materials, they also have some disadvantages that limit their use in organic synthesis. For example, the Claisen rearrangement strategy in most cases provides only ortho-allylic phenolic compounds and generally requires higher reaction temperatures (>200 ℃). Due to the electron-rich nature of phenols, Friedel-Craft type allylation of phenols typically results in multiple regioisomers (regioselectivity 20% -85%) or over allylated products, resulting in low yields (30-80%). In view of the widespread existence of allyl phenol in drug-related molecules, it is very necessary to develop a new method for obtaining allyl phenol compounds under mild conditions with high selectivity.
Disclosure of Invention
The invention aims to solve the technical problems of higher reaction temperature, lower selectivity and lower yield of allyl phenol compounds in synthesis in the prior art, and provides a preparation method of the allyl phenol compounds.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of allyl phenol compounds comprises the steps of reacting a mixed reaction system containing a diazoquinone compound, allyl borate, a catalyst and a solvent at room temperature in a protective atmosphere, and then separating to obtain the allyl phenol compounds.
Preferably, the diazoquinone compound has a structure shown in formula (I); the allyl borate has a structure shown in a formula (II); the allyl phenol compound has a structure shown in a formula (III);
wherein R1 is-CO2Me, -X, -OMe, -Me or-tBu; r2 is-Cl, -Br, -Me, -CH2OCH2Ph or-Ar; r3 is Me, cyclopropyl or cyclobutyl; r4 is Me, cyclopropyl or cyclobutyl.
Preferably, the concentration of the diazoquinone compound is 0.10-0.20 mmol/mL, and the concentration of the allyl borate ester is 0.30-0.60 mmol/mL.
Preferably, the concentration of the diazoquinone compound is 0.15mmol/mL and the concentration of the allylboronic acid ester is 0.45 mmol/mL.
Preferably, the catalyst is rhodium, Rh, α, α ', α' -tetramethyl-1, 3-benzenedipropionate2(esp)2。
Further preferably, the catalyst Rh2(esp)2The concentration of (b) is 0.002-0.004 mmol/mL.
Further preferably, the catalyst Rh2(esp)2The concentration of (3) was 0.003 mmol/mL.
Further preferably, the solvent is anhydrous dichloromethane DCM.
Still more preferably, the protective atmosphere is an argon atmosphere.
More preferably, the mixed reaction system further comprises
And (3) a molecular sieve.
The invention has the following beneficial effects: diazoquinone compounds and allyl boric acid ester in the invention are used as catalyst Rh2(esp)2Can be quickly carried out only under the conditions of room temperature and normal pressureThe allyl phenol compound is quickly and efficiently synthesized, the yield of the reaction can reach more than 85 percent, and the highest yield reaches 94 percent; and the reaction only produces allyl phenol compounds with single structures; therefore, the invention obviously reduces the reaction temperature for synthesizing the allyl phenol compound, and can be carried out efficiently only at room temperature (23 +/-2) DEG C; meanwhile, the yield of the allylphenol compound and the regioselectivity of the reaction are obviously improved.
Detailed Description
The present invention will be further described with reference to the following examples.
The reaction equation for preparing allylphenol compounds in the present invention is as follows:
wherein R1 is-CO2Me, -X, -OMe, -Me or-tBu; r2 is-Cl, -Br, -Me, -CH2OCH2Ph or-Ar; r3 is Me, cyclopropyl or cyclobutyl; r4 is Me, cyclopropyl or cyclobutyl.
Example 1
This example provides a method for preparing 4-allyl-3-fluorophenol by sequentially adding 4-diazo-3-fluorocyclohexyl-2, 5-dien-1-one (0.3mmol) and,
Molecular sieves (60mg), then anhydrous dichloromethane DCM (1.0mL) was added and stirred for 1 min, then allylboronic acid pinacol ester (0.9mmol, 3.0 equiv.) was added,
Rh2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 94% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ7.02(t,J＝8.5Hz, 1H),6.56(d,J＝9.9Hz,2H),5.93(ddt,J＝17.8,9.1,6.4Hz,1H),5.57(s, 1H),5.11–4.98(m,2H),3.32(d,J＝6.6Hz,2H).13C NMR(75MHz, CDCl3)δ155.2,136.3,131.1,118.9,115.7,111.1,103.3,102.9, 32.4.HR-MS(ESI):Calcd for C9H8FO-[M-H]-:151.0565；found: 151.0571.
example 2
This example provides a process for the preparation of 4-allyl-3-chlorophenol by charging 4-diazo-3-chlorocyclohexyl-2, 5-dien-1-one (0.3mmol) followed by anhydrous dichloromethane DCM (2.0mL) and stirring for 1 min in a 10mL Schlenk tube under an argon atmosphere, and charging allylboronic acid pinacol ester (0.9mmol, 3.0 equiv.), Rh2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 93% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ7.07(d,J＝8.3Hz, 1H),6.89(s,1H),6.71(d,J＝8.3Hz,1H),6.03–5.85(m,1H),5.70(s, 1H),5.15–4.97(m,2H),3.43(s,2H).13C NMR(75MHz,CDCl3)δ 154.5,136.0,134.4,131.1,129.9,116.5,116.1,114.22, 36.76.HR-MS(ESI):Calcd for C9H8ClO-[M-H]-:167.0269；found: 167.0270.
example 3
This example provides a method for preparing 4-allyl-3-bromophenol, by sequentially adding 4-diazo-3-bromocyclohexyl-2, 5-dien-1-one (0.3mmol) and (9/10 mL) into a Schlenk tube under argon atmosphere,
Molecular sieves (75mg), then dry dichloromethane DCM (1.0mL) was added and stirred for 1 min, then allylboronic acid pinacol ester (0.9mmol, 3.0 equiv.), Rh were added2(esp)2(2 mol%, 4.55mg) and dichloromethane (0.5 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 85% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ7.08(dd,J＝5.4, 2.7Hz,2H),6.75(dd,J＝8.4,2.5Hz,1H),5.94(ddt,J＝16.6,10.2,6.4 Hz,1H),5.17(s,1H),5.13–4.99(m,2H),3.43(d,J＝6.4Hz,2H).13C NMR(75MHz,CDCl3)δ154.5,136.1,131.0,124.5,119.6,116.2, 114.8,39.3.
example 4
This example provides a method for preparing methyl 2-allyl-5-hydroxybenzoate, in which 6-diazo-3-oxocyclohexyl-1, 4-diene-1-carboxylate (0.3mmol) and methyl 6-diazo-3-oxocyclohexyl-1, 4-diene-1-carboxylate (0.3mmol) are sequentially added into a 10mL Schlenk tube under argon atmosphere,
Molecular sieves (75mg) were then added with dry dichloromethane DCM (1).0mL) and stirred for 1 minute, and allylboronic acid pinacol ester (0.9mmol, 3.0 equiv.) and Rh were added2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 85% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ7.38(d,J＝2.7 Hz,1H),7.13(d,J＝8.3Hz,1H),6.95(dd,J＝8.3,2.7Hz,1H),6.05–5.88(m,1H),5.82(s,1H),5.07–4.90(m,2H),3.87(s,3H),3.65(d,J＝ 6.3Hz,2H).13C NMR(75MHz,CDCl3)δ168.5,154.1,137.8,133.3, 132.4,130.4,119.6,117.3,115.3,52.2,37.7.
example 5
This example provides a process for the preparation of 4-allyl-3-methoxyphenol by sequentially adding 4-diazo-3-methoxycyclohexyl-2, 5-dien-1-one (0.3mmol) followed by anhydrous dichloromethane DCM (1.0mL) and stirring for 1 min to a 10mL Schlenk tube under an argon atmosphere and adding allylboronic acid pinacol ester (0.9mmol, 3.0 equiv.), Rh2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction is finished, the reaction solution isThe reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 85% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ6.95(d,J＝8.0 Hz,1H),6.44–6.31(m,2H),6.04–5.87(m,1H),5.50(s,1H),5.07– 4.95(m,2H),3.78(s,3H),3.28(d,J＝6.4Hz,2H).13C NMR(75MHz, CDCl3)δ158.2,155.6,137.5,130.1,120.4,114.9,106.7,99.0,55.4, 33.6.
example 6
This example provides a method for preparing 4-allyl-3, 5-dimethylphenol, comprising sequentially adding 4-diazo-3, 5-dimethylcyclohexyl-2, 5-dien-1-one (0.3mmol) and a solvent in a 10mL Schlenk tube under argon atmosphere,
Molecular sieves (70mg), then dry dichloromethane DCM (1.0mL) was added and stirred for 1 min, then allylboronic acid pinacol ester (0.9mmol, 3.0 equiv.), Rh were added2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 85% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ6.53(s,2H), 5.97–5.79(m,1H),5.04–4.78(m,3H),3.32(d,J＝5.4Hz,2H),2.24(s, 6H).13C NMR(75MHz,CDCl3)δ153.3,138.2,135.7,114.7,32.9, 19.9.HR-MS(ESI):Calcd for C11H13O-[M-H]-:161.0972；found: 161.0959.
example 7
This example provides a method for preparing 4-allyl-2-chlorophenol by sequentially adding 2-chloro-4-diazoxycyclohexyl-2, 5-dien-1-one (0.3mmol) and,
Molecular sieves (60mg), then dry dichloromethane DCM (1.0mL) was added and stirred for 1 min, then allylboronic acid pinacol ester (0.9mmol, 3.0 equiv.), Rh were added2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 90% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ7.14(s,1H), 7.04–6.89(m,2H),5.90(ddd,J＝13.4,10.3,7.9Hz,1H),5.46(s,1H), 5.13–5.01(m,2H),3.30(d,J＝6.6Hz,2H).13C NMR(75MHz,CDCl3) δ149.6,137.0,133.3,128.8,128.6,119.7,116.1,116.1,39.1.
example 8
This example provides a process for the preparation of 4-allyl-2, 6-dichlorophenol by sequentially charging 2, 6-dichloro-4-diazocyclohexyl-2, 5-dien-1-one (0.3mmol) and,
Molecular sieves (70mg), then dry dichloromethane DCM (1.0mL) was added and stirred for 1 min, then allylboronic acid pinacol ester (0.9mmol, 3.0 equiv.), Rh were added2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 94% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ7.08(s,2H), 5.86(tdd,J＝20.4,13.5,4.1Hz,2H),5.16–5.01(m,2H),3.27(d,J＝ 6.7Hz,2H).13C NMR(75MHz,CDCl3)δ146.1,136.2,133.4,128.3, 120.9,116.8,38.8.HR-MS(ESI):Calcd for C9H7Cl2O-[M-H]-: 200.9879；found:200.9883.
example 9
The implementation provides a preparation method of 3-chloro-4- (2-methylallyl) phenol, which comprises the steps of sequentially adding 0.3mmol of 4-diazo-3-chlorocyclohexyl-2, 5-diene-1-ketone and 10mL of Schlenk tube in an argon atmosphere,
Molecular sieves (70mg), then dry dichloromethane DCM (1.0mL) was added and stirred for 1 min, then 2- (2-methylallyl) boronic acid pinacol ester (0.9mmol, 3.0 equiv.), Rh were added2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 86% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ7.07(d,J＝8.3 Hz,1H),6.89(d,J＝2.4Hz,1H),6.70(dd,J＝8.3,2.4Hz,1H),5.54(s, 1H),4.82(s,1H),4.60(s,1H),3.36(s,2H),1.73(s,3H).13C NMR(75 MHz,CDCl3)δ154.5,144.0,134.8,131.6,129.6,116.4,114.1,111.9, 40.5,22.4.HR-MS(ESI):Calcd for C10H10ClO-[M-H]-:181.0426；found: 181.0432.
example 10
This example provides a method for preparing 3-chloro-4- (2-chloroallyl) phenol, which comprises sequentially adding 4-diazo-3-chlorocyclohexyl-2, 5-dien-1-one (0.3mmol) and N-chloro-N-tert-butyl-N-ethyl (N-chloro-N-ethyl) in 10mL Schlenk tube under argon atmosphere,
Molecular sieves (70mg), then dry dichloromethane DCM (1.0mL) was added and stirred for 1 min, then 2- (2-chloroallyl) boronic acid pinacol ester (0.9mmol, 3.0 equiv.), Rh were added2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 85% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ7.15(d,J＝8.4 Hz,1H),6.90(d,J＝2.5Hz,1H),6.73(dd,J＝8.4,2.5Hz,1H),5.27(s, 1H),5.16(s,1H),5.05(s,1H),3.68(s,2H).13C NMR(75MHz,CDCl3)δ 155.3,140.0,135.0,131.9,126.8,116.6,114.2,113.8,42.0.HR-MS (ESI):Calcd for C9H7Cl2O-[M-H]-:200.9879；found:200.9881.
example 11
This example provides a method for preparing 3-chloro-4- (2- (4-chlorophenyl) allyl) phenol, which comprises sequentially adding 4-diazo-3-chlorocyclohexyl-2, 5-dien-1-one (0.3mmol) and (2.3 mmol) into a 10mL Schlenk tube under argon atmosphere,
Molecular sieves (60mg), then anhydrous dichloromethane DCM (1.0mL) was added and stirred for 1 min, then 2- (4-chlorophenyl) propylboronic acid pinacol ester (0.9mmol, 3.0 equiv.), Rh were added2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 85% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ7.36(d,J＝8.6 Hz,2H),7.27(d,J＝6.6Hz,2H),7.04(d,J＝8.4Hz,1H),6.89(d,J＝ 2.5Hz,1H),6.65(dd,J＝8.4,2.5Hz,1H),5.46(s,1H),4.95(s,1H), 4.91(s,1H),3.81(s,2H).13C NMR(75MHz,CDCl3)δ154.7,144.8, 139.1,134.7,133.3,131.4,128.8,128.4,127.4,116.4,114.9,114.2, 37.8.HR-MS(ESI):Calcd for C15H11Cl2O-[M-H]-:277.0192；found: 277.0208.
example 12
This example provides a method for preparing 3-chloro-4- (2-naphthylallyl) phenol, which comprises sequentially adding 4-diazo-3-chlorocyclohexyl-2, 5-diene-1-one (0.3mmol) and phenol in a 10mL Schlenk tube under argon atmosphere,
Molecular sieves (70mg), then dry dichloromethane DCM (1.0mL) was added and stirred for 1 min, then 2- (2-naphthylallyl) boronic acid pinacol ester (0.9mmol, 3.0 equiv.), Rh2(esp)2(2 mol%, 4.55mg) and dichloromethane (1.0 mL). The reaction mixture was then stirred at room temperature under normal pressure until complete diazoquinone consumption was monitored by TLC analysis, and after the reaction was complete, the product was formed as detected by TLC plates.
The reaction equation is as follows:
after the reaction was complete, the reaction mixture was filtered and washed with dichloromethane (20mL), spun dry, and the residue was isolated by passage through a silica gel column to give the product as a pale yellow oil in 85% yield with the following nuclear magnetic data:1H NMR(300MHz,CDCl3)δ7.87–7.78(m, 4H),7.67–7.61(m,1H),7.47–7.42(m,2H),7.10(d,J＝8.4Hz,1H), 6.90(d,J＝2.5Hz,1H),6.63(dd,J＝8.4,2.5Hz,1H),5.64(s,1H),5.00 (s,1H),3.97(s,2H).13C NMR(75MHz,CDCl3)δ154.7,145.7,137.9, 134.7,133.4,132.9,131.5,129.2,128.3,127.9,127.5,126.2,125.9, 124.8,124.5,116.4,114.9,114.2,37.9.HR-MS(ESI):Calcd for C19H14ClO-[M-H]-:293.0739；found:293.0748.
in conclusion, the preparation method of the allyl phenol compound is simple, the reaction conditions are mild, the allyl phenol compound can be quickly and efficiently synthesized only under the conditions of room temperature and normal pressure, the yield can reach more than 90%, and the reaction only generates the allyl phenol compound with a single structure; therefore, the preparation method of the allyl phenol compound has wide application prospect in the field of medicine preparation.
The present description is to be considered as illustrative and not restrictive, and it is within the scope of the present invention that certain changes and modifications may be made in the details of the invention without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of allyl phenol compounds is characterized in that a mixed reaction system containing a diazoquinone compound, allyl borate, a catalyst and a solvent is reacted at room temperature in a protective atmosphere, and then the allyl phenol compounds are prepared by separation.
2. The preparation method according to claim 1, wherein the diazoquinone compound has a structure represented by formula (I); the allyl borate has a structure shown in a formula (II); the allyl phenol compound has a structure shown in a formula (III);
wherein R1 is-CO2Me, -X, -OMe, -Me or-tBu; r2 is-Cl, -Br, -Me, -CH2OCH2Ph or-Ar; r3 is Me, cyclopropyl or cyclobutyl; r4 is Me, cyclopropyl or cyclobutyl.
3. The method according to claim 1 or 2, wherein the concentration of the diazoquinone compound is 0.10 to 0.20mmol/mL, and the concentration of the allylboronic acid ester is 0.30 to 0.60 mmol/mL.
4. The production method according to claim 3, wherein the concentration of the diazoquinone compound is 0.15mmol/mL, and the concentration of the allylboronic acid ester is 0.45 mmol/mL.
5. The method according to claim 1, wherein the catalyst is rhodium, Rh, α, α ', α' -tetramethyl-1, 3-benzenedipropionate2(esp)2。
6. The production method according to claim 5, wherein the catalyst Rh is2(esp)2The concentration of (b) is 0.002-0.004 mmol/mL.
7. The production method according to claim 6, wherein the catalyst Rh is2(esp)2The concentration of (3) was 0.003 mmol/mL.
8. The method of claim 1, wherein the solvent is dry dichloromethane DCM.
9. The method of claim 1, wherein the protective atmosphere is an argon atmosphere.
10. The method according to claim 1, wherein the mixed reaction system further comprises
And (3) a molecular sieve.
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| CN114805093B (en) * | 2022-05-12 | 2023-04-25 | 暨南大学 | Preparation method of diarylamines |
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